Manganesetricarbonyl



United States Patent 3 290,344 [(ACETONYLSULFONYDCYCLOPENTADIENYL] MANGANESETRICARBONYL John Kozikowski, Walled Lake, Mich., and Michael Cais,

This process is illustrated by way of the following reaction:

Haifa, Israel, assignors to Ethyl Corporation, New 5 York, N.Y., a corporation of Virginia No Drawing. Qriginal application Aug 12, 1960, Ser. No.

Dmded and aPPhcatlon May 1963 In the above reaction, R is an alkyl or aralkyl group, h (e1 260 429) and X is a halogen. The reaction conditions employed are not critical and the alkyl or aralkyl halide, when This application is a division of application Serial No. used in sufiicient excess, may itself serve as the solvent. 49,135, filed August 12, 1960, now abandoned. To further illustrate our invention, there is presented the This invention relates to a variety of organometallic f l g g n exa ple a d tables W h m r z compounds and the processes employed i their d the results obtained from several such reactions. tion. More specifically, tlllis inrilention rfelates tlo com- 15 Example 1 on nd rocesses invo vin t use 0 c c entadien y l si ilfon ic acid manganese trisarbonyl oni po ii nd. g sodium Salt. delgvatlve of gy g g sulfimc An object of our invention is to provide new organoam manganese t-ncar Onyl was 1580 ved m et anol and refluxed with a shght excess of the alkyl or aralkyl halide. metallic compounds and processes for their pr p The cooled mixture was filtered to remove the sodium Afurther Provlde e halide which formed, and the ethanolic filtrate was conmcafPonyl derlvatlvfi and PmcesmS for f centrated by heating until crystals began to appear. After Addltlonal oblects will become apparent from a readlng cooling, the crystals were collected and were generally of the Specification and claim which followof a high degree of purity. An additional crop of crystals The objects of this invention are accomplished by could be obtained by diluting the ethanolic mother liquor preparing a wide variety of cyclopentadienyl manganese ith t tricarbonyl sulfone compounds. These compounds are Following the general procedure set forth in the precedf-ormed by reacting a cycl-opentadienyl sulfinic acid m-aning example, the results were obtained as set forth in the ganese tricarbonyl with an alkali metal hydroxide or an following Table I. The analyses obtained for the comalkali metal salt of an acid which is weaker than the cyclopounds of Table I are set forth in Table II.

TABLE I Reflux Compound Obtained Yield Ml. C. Recrystn. R--X Time, hrs. Percent Solvent CH3I 2 [(llethsgsulfiinyl)cyclopentadienyl] manganese 97 156-158 B.1 OlCHz[(CHa)sC]2C5HzOH 20 [(33%5t i hutyl-4-hydroxybenzylsulionyl) 84 170-171 E.1

cyclopentadienyl] manganese tricarbonyl. CH3COCHzC1 3 2 [Acetonylsulfonybcyclopentadienyl] 75 123-124 B.

manganese tricarbonyl. BrCH2COC5H4Mn(CO)3 3 lll(Tricarbonylmanganese)cyclopentadienyl] 94 167-168 E/B.

carbonyl methylsulionyl) cyclopentadienyl] manganese tricarbonyl.

1 B, benzene; E, ethanol. 2 2,6-di-tert-butyl-a-ehloro-p-cresol. 3 The 2,4-dinitrophenylhydrazone of [(p-methoxyphenylsulfonyl)cyclopentadienyl] manganese tricarbonyl formed very readily, M.P. 190-191 (from chloroform/methanol). Analysis, calcd. for C17H1aMnN4O S: C, 40.4; H, 2.57; Mn, 10.9. Found: C, 40.5;

H, 2.60; Mn, 10 9 4 (Bromoacet ylcyclopentadienyl) manganese tricarbonyl.

TABLE II Compounds Carbon Percent Hydrogen Percent Manganese Percent Sulfur Percent Calcd. Found Calcd. Found Calc Found Caled. Found [(Methylsulfonyl) cyclopentadienyl] manganese tricarbonyl 38. 3 37. 9 2. 2. 42 19. 4 19. 4 11.3 11. 6 [(3,5-di-tert-butyl-4-hydroxybenzylsulfonyl) cyclopentadienyl] manganese tricarbonyl 56. 8 56. 8 5. 63 5. 66 11. 3 11. 3 6. 6 6. 6 (Acetonylsulfonyl) cyclopentadienyl] manganese tricarbonyl 16. 9 16. 9 {[Tricarbonylrnang anese) eyclopentadienyl] carbonyl methylsulionyl} cyclopentadienyl} manganese tricarbonyl 42. 1 42. 2 l. 95 2. 19 21. 4 21. 5 6. 28 6. 24

pentadienyl sulfinic acid manganese tricarbonyl reactant.

As a result, there is formed a salt having the formula SO2Z Rx M11(CO)3 Bnonroacetylcyclopentadienyl manganese tricarbonyl, which was employed as a reactant, as reported in Table I, was prepared by reacting an acylcyclopentadienyl manganese tricarbonyl compound having the formula in which R is a univalent hydrocarbon radical containing from one to about eight carbon atoms and x is an integer ranging from zero to three, with a halogenating agent. In the specific case of the bromoacetyl compound, the halogenating agent was bromine. Analogous compounds such as the chloroacetylcyclopentadienyl manganese tricarbonyl and iodoacetylcyclopentadienyl manganese tricarbonyl compounds are prepared by reaction of chlorine or iodine with an acetylcyclopentadienyl manganese tricarbonyl compound. The reaction can be conducted in any inert solvent, although preferably, the solvent is polar and most preferably, it is an ether. The reaction is conducted at low temperatures in the order of about C. To illustrate the reaction, there is presented the following example.

Example II To a solution comprising 24.6 grams of acetylcyclopentadienyl manganese tricarbonyl in 250 ml. of ether cooled to 0 C. was added 16.0 grams of bromine. The bromine 'was added dropwise with stirring over a one-half hour period. Stirring was continued for an additional one-half hour after which the ether and hydrogen bromide were removed by distillation of the reaction mixture at reduced pressure. The yellow-orange compound (bromoacetylcyclopentadienyl manganese tricarbonyl) which remained was recrystallized from ether and was found to be soluble in organic solvents. The yield was 27 grams of bromoacetylcycl-opentadienyl manganese tricarbonyl or 83 percent of theory. The compound had a melting point of 75-77" C. and on analysis there was found: C, 37.1; H, 1.93; Mn, 17.0; Br, 24.8 percent. Calculated for C H MnO Br: C, 36.9; H, 1.85; Mn, 16.9; Br, 24.6 percent.

The preparation of cyclopentadienyl sulfinic acid manganese tricarbonyl which is employed as a starting material in preparing the compounds of this invention, as well as the preparation of other related cyclopentadienyl manganese tricarbonyl compounds, is fully described in our .copending patent application Serial No. 283,139, filed May 13, 1963, now US. Patent No. 3,205,245, issued September 7, 1965.

Among the important uses of our compounds is their use as fuel and oil additives. For example, they are useful antiknocks when added to gasoline. They may be used as primary antiknocks in which they are the major antiknock component in the fuel or as supplemental antiknocks. When used as supplemental antiknocks, they are present as the minor antiknock component in the fuel in addition to a primary antiknock such as a tetraalkyllead compound. Typical alkyllead compounds are tetraethyllead, tetrabutyllead, tetramethyllead and various mixed lead alkyls such as dimethyldiethyllead, diethyldibutyllead and the like. When used as either a supplemental or primary antiknock, our compounds may be present in the gasoline in combination with typical scavengers such as ethylene dichloride, ethylene dibromide, tricresylphosphate, trimethylphosphate and the like.

The compounds of our invention have further utility as additives to residual and distillate fuels generally, e.g., jet fuels, home heater fuels and diesel fuels, to reduce smoke and/or soot formation. Also, they may be employed as additives to lubricating oils in which case they act to improve the lubricity of the base oil.

Our compounds are further useful in many metal plating applications. In order to effect metal plating using the compounds, they are decomposed in an evacuated space containing the object to be plated. On decomposition, they lay down a film of metal on the object. The gaseous plating may be carried out in the presence of an inert gas so to prevent oxidation of the plating metal or the object to be plated during the plating operations.

The gaseous plating technique described above finds wide application in forming coatings which are not only decorative but also protect the underlying substrate material.

Deposition of metal on a glass cloth illustrates the applied process. A glass cloth band weighing one gram is dried for one hour in an oven at C. It is then placed in a tube which is devoid of air and there is added to the tube 0.5 gram of [(methylsulfonyl)cyclopentadienyl] manganese tricarbonyl. The tube is heated at 400 C. for one hour after which time it is cooled and opened. The cloth has a uniform metallic grey appearance and eX- hibits a gain in weight of about 0.02 gram.

A further utility for our compounds is as drying agents in which case the compounds are incorporated in paints, varnish, printing inks, synthetic resins of the drying oil type, oil enamels and the like. A still further utility for our compounds is their use as chemical intermediates in the preparation of metal-containing polymeric materials or in the preparation of new organic materials.

Having fully defined the novel compounds of our invention, their mode of preparation and their many utilities, we desire to be limited only within the lawful scope of the appended claim.

We claim:

[(Acetonylsulfonyl)cyclopentadienyl] manganese tricarbonyl.

No references cited.

HELEN M. MCCARTHY, Primary Examiner.

A. P. DEMERS, Assistant Examiner. 

